Acrylonitrile-vinylidene chloride terpolymers



United States Patent "ice 3,424,731

Patented Jan. 28, 1969 3 424 731 third components are efficacious inmodifying and im- 5 proving the properties of the resulting terpolymers.The ACRYLONITRILE-VINYLIDENE CHLORIDE TERPOLYMERS particular branchedchain third components are char- Alden Edward Blood James Davis Hellerand Hugh J acterized by unusually good resistance to thermal degrada-Hagemeyer, Longview Tex assignors to Eastman 5 tion and hydrolysis asillustrated by the following Ex- Kodak Company, Rochester, N.Y., acorporation of amples A and New Jerse N0 Drawing Continuation-in-part ofapplication Ser. No. Examp 1e A' Thermal stablhty 221,368, Sept. 4,1962. This application Nov. 1, 1965, The thermal stabilities of theterpolymers consisting of Ser. No. 505,973 30 percent acrylonitrile, 60percent vinylidene chloride US. Cl. 260-8081 6 Claims 10 and 10 percentR (a vinyl ester), by weight based on CL /40 total monomer weredetermined by placing compressionmolded buttons 1 inch in diameter and4; inch thick in an oven at 100 C. If after 1 hour no change was seenABSTRACT OF THE DISCLOSURE in the sample, the oven temperature wasincreased C.

Resinous terpolymers comprising vinylidene chloride, 15 When a sampleshowed evidence of change, it was reacrylonitrile and a polymerizablemonomer selected from moved and analyzed. If a sample showed no evidenceof the group of vinyl 2,2-dimethylalkanoate, 2,2-dirnethylchange and thetemperature and time dilferences were butyrate, and2,2-dimethylhexanoate. Also disclosed is significant considering allsamples tested, the remaining process of preparing the terpolymers. 20sample was removed and examined. In the tables below,

VP represents vinyl propionate, VB vinyl butyrate, VDB vinyl2,2-dimethylbutyrate, and VI vinyl isobutyrate.

COMPARATIVE THERMAL STABILITY OF TERPOLYMERS AN/60% VCl2/10% R] MaximumBar Softening Rockwell Total Oven Point, C. Hardness Color R ExposureTemper- (R Scale) Time, hr. atnre,

C Before After Before After Before After 1 100 81 75 110 85 YellowBrown. 1 100 85 so 110 83 do Do. 4 160 90 88 112 105 do l Yellow. 1 I0083 77 I11 84 do Brown.

This application is a continuation-in-part of my copend- ExampleB.-Hydrolytic stability mg application Ser. No. 221,368, Blood of al.,filed Sept. Comparisons of hydrolytic Stability were made by Paibandonedimmersing molded polymer buttons as described above Th sinvention relates to improved resinouswinylldene in boiling 10 percentNaOH Changes in appearance of ghloride terpolymers, and to a process fortheir preparathe button evidence polymer degradation The new vinylidenechloride terpoly-mers of the inveniggfififi STABILITY OF tion have thefollowing by weight composition ranges: [30% AN/60% V012[10% N Percent RHours in Caustic Appearance Vinylidene chloride 55-87 8 CrackedAcrylonitnle 10-40 2 N 1?]0. Third polymerizable monomer 3-15 15 f g gglthat is, they contain recurring vinylidene chloride unit It isparticularly noteworthy that the specific 2,2- recurring acrylonitrileunits and recurring monomeric units dimethy Substltlltlon as contrastedx p to the in the proportions above stated, the total of these unitsvlnyl lsoblltyfate 0f the abPVe exampks 0r f alkyl equalling 100% forany specific terpolymer of the i substitutions results in strikingimprovements in thermal tion. and hydrolytic stability. Such effects arequite unpre- However, we have found that not all polymerizable dictablewhen compared to those obtained from other monomers are suitable a thethird component To roseemingly equivalent substitutions or when viewedin the duce the advantageous terpolymers of the invention, this light ofteachings in the art. third component must be one selected from a verylimited If the g cofnposltlon ranges a e exceeded for any groupconsisting of vinyl 2,2-dimethylalkanoates wherein of the threespecified components, the resulting product the dimethylalkanoate groupcontains from 5-8 carbon is brittle and has no strength. The softeningpoint can be atoms, e.g., vinyl 2,2-dimethylpropionate, vinyl 2,2-varied from about 95 C. b y varyingthe acrylonitrile dimethyl'butyrate,vinyl 2,2-dirnethylhexanoate, etc., vinyl 60 content. The productscontaining the higher percentage alkyl ethers wherein the alkyl groupcontains from l-8 of acrylonitrile have the highest softening point and,concarbon atoms, e.g., vinyl methyl ether, vinyl butyl ether, versely,the lower percentages of acrylonitrile gi've prodvinyl2,2-dimethylpropyl ether, vinyl 2,2-dimethylbutyl ucts having the lowersoftening points. Terpolymers conether, etc., alkyl acrylates andmethacrylates wherein the taining less than the specified 10% ofacrylonitrile are too alkyl group contains from 1-8 carbon atoms, e. g.,methyl soft, while those containing more than 40% of acryloniacrylate,n-butyl acrylate, methyl methacrylate, n-propyl trile become moreinsoluble, the acetone solubility being methacrylate, 2,2-dimethylpropylacrylate, 2,2-dimethylpractically negligible at the higher acrylonitrileconcentrabutyl acrylate, etc., and dialkyl fumarates and maleates tions.However, all of the products of the invention have wherein the alkylgroup contains from 1-8 carbon atoms, high strength and stiffness,provided the above specified e.g. dimethyl fumarate, di-n-butylfumarate, di-2,2- 7O composition ranges are not exceeded. Those vinyl2,2- dimethylbutyl fu marate, etc. and the correspondingmaledimethylalkanoate-containing terpolylmers have parates. As little as3% and not more than 15% of these ticularly useful properties and arepreferred.

The resinous terpolymers of the invention above defined have thefollowing combination of properties:

(1) High strength and toughness. (2) Very high stiffness.

Normal or higher than atmospheric pressures can be used. Advantageously,the reactions can be carried out under an inert atmosphere, e.g., undernitrogen. For emulsion polymerizations any nonsolvent can be employed,water being especially advantageous. The monomers can be emulsified inwater using emulsifying agents such as salts of higher fatty acids, e.g.sodium or potassium stearate, pahnitate, etc., or ordinary soaps, orsalts of higher fatty $23k?gfigfigg g 5 alcohol sulfates, e.g. sodium orpotassium lauryl sulfate, LOW sofgtening p i sodium or potasslumdi(2-ethylhexyl) sulfosuccinate, so- Acetone solubility chum orpotassium cetyl sulfate, sod um or potass um ste- Good low tem era'tureProperties aryl sulfate, etc., or salts of aromatic sulfonic acids, e.g.I'm ervious topwater Va or 10 sodium or potassium salts ofalkylnaphthalene sulfonic p p acids, higher molecular weight quaternaryammonium This Combination of Properties Permits coatings to he Salts,e.g. dimethyl benzylphenyl ammonium chloride, and made therefrom ontopaper, fabrics and other p the like. If desired, an activating agent canbe added such ture-sensitive materials. The coated articles are strong,a an lk li metal bi ulfit Sodium or potassium flexible and impervious towater vapor. Such coatings can sulfite, in about similar amount as thecatalyst. Also, be made from emulsions or solutions of the terpolymers.chain regulators such as alkyl mercaptans, e.g. lauryl mer- AlSO, the10W SOftGIlil'lg points permit the coatings to be captan, can be furtheradded with advantage to the mixheat set so as to form firm bonds to thesupport material. tllfe. The terpolymeric-products produced a aboveSheets and molded articles can also be P p Which scribed are thenisolated from their polymerization reacare tough and very strong andrigid. tion mixtures by conventional separation means for poly- Incontrast to the above, compositions containing only mers, for example,by precipitation, coagulation, filtravinylidene chloride andacrylonitrile, or vinyl chloride tion, etc. In general, the terpolymercompositions are and acrylonitrile, or compositions containingacrylonitrile, approximately the same as the monomer compositionvinylidene chloride and a different third compatible monocharged over awide range of conversions. mer outside of the composition limits of theinvention, Th bov ti d monomeric i l 2,2-di th 1- are brittle and weakand wholly unsuited for coating or alk t may b prepared b h generalmethod d making sheet and molded articles. None of the composiib d by R,R, Ad lman, J Org, Chem, 14, 1057-77 tions previously described intheprior art have the unique (1949); the 2,2-dimethylalkyl acrylates andmethacry- Combination of Properties p ssed by the terpolymer lates bythe general method of J. W. Crawford, J. Soc. compositions of theinvention. Chem. Ind., 68, 201-208 (1949); and the vinyl 2,2-di- It is,accordingly, an object of the invention to provide methylalkyl ethers bythe method described in our conew resinous, acetone-soluble vinylidenechloride terpolypending application Ser. No. 184,493, filed Apr. 2,1962. mers having softening points from about 6095 C. An- The followingexamples will serve to illustrate further other object is to providecoating and molding composithe terpolymers of the invention, and themanner of pretions of the same. Another object is to provide shapedparing the same. articles therewith. Other objects will become apparentExamples 1-13 from the dcscriptich and c c These examples were carriedout by emulsion polym- In accordance Wlth h lhvchhch Wc Prepare thercslh' erization technique. The procedure used with Example 1 0115terpplymers Offhe mvenfioq a above defined by is described below indetail. All of the other examples polymerlzlug ImXtllfe P p from y 40were carried out in the same way with appropriate re- Weight Ph ychlol'ldc, from 9- by Wclght of actant and concentration changes. Theresults are all acrylchmhehhd frclh 3-15 Y Wclght of one ohmorctabulated in the table following the detailed example. of the mchhchcdthlrd polymchzahlc mohomcrs 1n the In a 450-ml. Parr pressure vesselwere charged 180 ml. presence of a conventional polymerization catalyst.Heat f distilled water, 5 g, f acrylonitrile, 34.0 f vinyland actiniclight such as ultraviolet radiation also acceleridene chloride, 20 ofvinyl zzdimethylhexanoam, 22 ate the rcactich- Ahy mcthcd f h to the arth he g. of Duponol ME (a fatty alcohol sulfate), 0.1 g. of soused, forexample, polymerization in mass, suspension, dium bisulfite, 0.8 g. ofsodium persulfate, 3 drops of emulsion, solution, etc. Suitablepolymerization catalysts dodecyl mercaptan and 5 drops f trimethylamine1 includes peroxides c as hydrogen Peroxide: hchzcyl tion in water. Theair was displaced with nitrogen and P i acctyl PcrOXldc, lahl'cyl P iditcrthhtyl the bottle was heated at 60 C. with shaking for 24 hours.pcrcxlfic etc-i Pcrshlfatcs Such as ammohlhmgscdlhm ahd The resultingemulsion was precipitated with saturated Potasslum Pershlfatcs,Pcrhcratcs Such as Sodhhh and P sodium chloride solution. Theprecipitated polymer was tassium perborates, persulfinic acid,water-soluble salts Washed with Water and methanol, and then dried at 4of sulfo-per-acids (e.g. Caros acid), and the like. Other under vacuumThe yield f polymer was 3 g or catalysts such as boron trifluoride,azines, ketazines, etc. a conversion to polymer f 5 5 Analysis f thispo1y can also be used. Mixtures of these catalysts may be emf chlorineand nitrogen contents indicated f Plcycd, 1f dcshcd- The total amountchcatalyst can Vary these results that it was a terpolymer of thecomposition from ahhht to 3%, based on the Wclght of the mono listed inTable 1 below. A button made from 1.0 g. of filers t0 be p y Thetemperature of the reaction the above terpolymer using a moldtemperature of 160 can vary widely, but preferably about from 30125 C.C. was light yellow in color, acetone-soluble, and extremely tough andstrong and hard. The softening point (S.P in the table) was found to be62 C. as measured on a melting point bar.

TABLE 1.TERPOLYMER COMPOSITION, WEIGHT PERCENT AN V1011 Third MonomerConver., Physical S.P.,

Percent Description C.

12. 5 82. 7 Vinyl 2,2-dimethylhexanoate, 4.8... 85. 5 Tough 62 7. 6 66.5 Vinyl 2,2-dimethy1butyrate, 5.9 78. 0 Very tough. 86 3. 3 58. 4 Vinyl2,2-dimethylbutyrate, 8.3 83. 6 Tough 91 3. 0 60. 0 2 2-dimethylaerylate, 7.0 91. 3 2. 2 61. 2 inyl 2,2dimethylbutyl ether, 6 81. 6 8.858. 4 Vinyl 2,2-dimethylbutyrate, 12. 83. 0 30. 1 63. 2 Methylmethacrylate, 6.7 92. 0 22. 0 74. 8 Dibutyl maleate, 3.2 82. 1 63. 2 22.6 Vinyl 2,2dimethy1butyrate, 14.2.-. 79.0 44. 7 44. 7 Vinyl2,2-dimethylbutyrate, 10.6 80.0 16. 3 56. 2 Vinyl 2,2-dimethylbutyrate,27.5-- 80.0 8. 0 82. 0 Methyl methacrylate, 10.0. 61.0 13 45. 5 54. 5None 80.0

Two large scale polymerizations were carried out in a one-gallonautoclave to obtain enough product for more complete propertyevaluation. The runs were carried out by the general process describedin Example 1 with the obvious necessary changes. The products and theirproperties are described in the following Table 2.

TABLE 2 Example 14 Example Polymer Comp, by wt.:

Percent Acrylonitrile 34. 5 28. 7

Percent Vinylidene Chloride 58. 5 66.5

Percent V06 ester 1 7. 0 4. 8 Bar Softening Point, C-.. 90. 0 78.0 VicatSoftening Point, C. 79. 6 66. 6

Tensile Strength, p.s.i Brittleness Temp, C 32 32 Stiffness in Flexure,p.s.' 439, 100 404, 700 Rockwell Hardness, R Scale..- 11 101 IzodImpact, ft. lbs/in. of notch 0. 0 43 Acetone Solubility, 30% cone 1Vinyl 2,2-dirnethylbutyrate.

Soluble.

These properties (listed in above Table 2) show the unique combinationof high tensile strength, good impact strength, extremely highstiffness, high hardness, low softening point and acetone solubility. Itis to be noted that these properties were measured at a temperaturebelow the brittle temperature. Thus, the properties are little affectedat lower temperatures.

Other generally similar terpolymers of the invention may be prepared bysubstituting into the above examples any of the mentioned suitable thirdcomponents such as, for example, vinyl 2,2-dimethylpropionate, vinyl2,2- dimethylpentanoate, 2,2-dimethylpropyl ether, 2,2-dimethylmethacrylate, n-butyl acrylate, n-butyl methacrylate, etc. While theexamples have illustrated only molded buttons prepared from theterpolymers of the invention, it will be understood that other moldedarticles, and coatings, films and sheets of similarly advantageousproperties can only be made therefrom. Solutions and compositions of theterpolymers may also have incorporated therein, if desired, othermaterials such as fillers, pigments, dyes, etc., to give added effectsand utility to the coatings and articles produced with theseterpolymers.

What we claim is:

1. A resinous terpolymer of (1) from 55-87% by 6 weight of vinylidenechloride, (2) from 10-40% by Weight of acrylonitrile and (3) from 3-15%by weight of a vinyl, 2,2-dimethylalkanoate wherein the saiddimethylalkanoate group contains from 5-8 carbon atoms, the total ofsaid (1), (2) and (3) being equal to 100%.

2. A resinous terpolymer of (1) from -87% by weight of vinylidenechloride, (2) from 10-40% by weight of acrylonitrile and (3) from 3-15by weight of vinyl 2,2-dimethyl'butyrate, the total of said (1), (2) and(3) being equal to 3. A resinous terpolymer of (1) from 55-87% by weightof vinylidene chloride, (2) from 10-40%' by weight of acrylonitrile and(3) from 3-15% by weight of vinyl 2,2-dimethylhexanoate, the total ofsaid (1), (2) and (3) being equal to 100%.

4. A process for preparing a resinous terpolymer of vinylidene chloride,acrylonitrile and a vinyl 2,2-dimethylalkanoate which comprises heatingat a temperature of from 30-125 C. and in the presence of a peroxidepoly-merization catalyst, a mixture containing as the sole polymerizablecomponents (1) from 55-87% by weight of vinylidene chloride, (2) from10-40% by weight of acrylonitrile and (3) from 3-15 by weight of a vinyl2,2-dimethylalkanoate, wherein the said dimethylalkanoate group containsfrom 5-8 carbon atoms.

5. A process for preparing a resinous terpolymer of vinylidene chloride,acryl-onitrile and vinyl 2,2-dimethylbutyrate which comprises heating ata temperature of from 30-125 C. and in the presence of a peroxidepolymerization catalyst, a mixture containing as the sole polymerizablecomponents (1) from 55-87% by weight of vinylidene chloride, (2) from10-40% by weight of acrylonitrile and (3) from 3-15% by weight of vinyl2,2-dimethylbutyrate.

6. A process for preparing a resinous terpolymer of vinylidene chloride,acrylonitrile and vinyl 2,2-dimethylhexanoate which comprises heating ata temperature of from 30-125 C., a mixture containing as the solepolymerizable components (1) from 55-87% by weight of vinylidenechloride, (2) from 10-40% by weight of acrylonitrile and from 3-15 byweight of vinyl 2,2-dimethylhexanoate.

References Cited UNITED STATES PATENTS 7/1952 Wolf 260-785 4/1942 Arnold260-87] XR

